Co-crz-br



United States Patent 26,178 METHOD OF CONTROLLING MICROORGANISMS WITHZ-HALO-SUBSTITUTED ACETOPHENONES George E. Lukes, Kentfield, and ThomasB. Williamson,

Santa Clara, Caliii, assignors to Staulfer Chemical 5 Company, New York,N.Y., a corporation of Delaware N0 Drawing. Original No. 3,184,379,dated May 18. 1965, Ser. No. 172,849, Feb. 13, 1962. Application forreissue Oct. 4, 1965, Ser. No. 493,309

6 Claims. (Cl. 167-30) Matter enclosed in heavy brackets appears in theoriginal patent but forms no part of this reissue specification; matterprinted in italics indicates the additions made by reissue.

This invention pertains to a method of controlling pest microorganismsby contacting them with certain substituted Z-halomethyl aryl ketones.The invention is also concerned with the preparation, use andapplication of biocidally active compositions containing as the toxiccomponent thereof at least one of the aforementioned halomethyl arylketones.

The present invention is predicated on the finding that certainhalomethyl aryl ketones, particularly 2-bromoacetophenones, are highlytoxic to microorganisms of the type which affect commercial food crops.We have, for instance, ascertained that these chemical compounds areespecially effective in combating certain varieties of destructive soilfungi such as Rhizoctonia solani, Fusarium solani and the like. Otherdeleterious microorganisms which are susceptible to the toxicants of the3 invention include bacteria and, in this case, reference is made toAspcrgillus niger, Penicillium and Escherichia coli.

The halomethyl aryl ketones, the biocidal properties and use of whichare contemplated herein, can be depicted by the following formulae:

C 0CII2 X 4 and COOH:X

wherein R R R and R designate hydrogen, a lower alkyl radical, a loweralkoxyl radical, amino, nitro and halogen e.g. fluorine, chlorine orbromine, it being understood at least one of said R R R and R is asubstituent other than hydrogen and X can be chlorine or bromine.Specific configurations falling within the ambit of Formulae I and IIare exemplified in the list of structures below:

Compound 1 HaC CO CIII BI' GHQ Compound 2 Re. 26,178 Reissued Mar. 21,1967 Compound 3 Compound 4 on, C 0on,nr

Compound 5 n,o- 4: OCH2BI Compound 6 c H, Q-o o-o urn;

Compound 7 c1- -0 o-on, nr

Compound 8 a c OCI-I]3r Compound 9 oils-Go o-o Hi-Bt Compound 11Compound 12 Compound 13 11.0 oo 0-0 Ha-Br Compound 14 @CMM l CH;

3 Compound Compound 16 Compound 17 Compound 1 8 Compound 19 Compound 20Compound 21 Compound 22 Compound 23 (1H3 (llll l C Ii: C H:

Compound 24 o c in 0 Hz Compound 25 O CH:

Compound 26 0 (l; in

OCII

OCH

may be encountered wherein the halogenation proceeds at an impracticallylow velocity and, in such instances, the reaction is accelerated by theuse of catalysts, and for this purpose, certain anhydrous heavy metalsalt halides, i.e. ferric chloride, zinc chloride etc. are especiallyefiicacious. An alternate procedure whereby one may arrive at thecompounds of the invention comprises the chloroacetylation of therequisite aromatic ring compound having the appropriate number andarrangement of substituents. Further details of the aforedisclosedreactions can be had by resorting to the original technical literatureof which the various chemical journals and patent literature areparticularly useful.

In using the 2-halomethyl aryl ketones as contemplated herein, it ismerely necessary to contact, with these toxicants, the microorganism,the growth of which it is desired to control. This can be accomplishedby a variety of procedures which are known to the art. For instance, asolution of the compound in an organic solvent may be applied directlyto the soil in the form of a spray. Alternately dispersions of thecompounds in a water media may be advantageously employed. In the lattercase, the use of various surface active agents or soaps may be desirablefor the purpose of stabilizing the dispersions. Since the compounds ofthe invention have been found to be nonphyto-toxic, the non-volatilerepresentatives can be mixed with talc or other inert binder and theresultant mixture combined with the cotton or bean seed before plantinginto fungus infected soil. Fumigation techniques may also be resorted toif the volatility of the compound is sufiiciently high. The biocidalactivity of the compounds of the invention are set forth in the tablebelow:

In ascertaining the bactericidal activity of the herein contemplatedcompounds, 1 oz. bottles were partially filled with 10 ml. of malt ornutrient broth, the containers capped with aluminum foil, sterilized anda solution of the compound to be tested injected by means of a syringethrough the foil into the broth. Water suspensions of such typicalbacteria as Aspergillus niger, Penicillium and Escherichia coli wereinjected into the broth and the botties sealed and held for one week,after which the bacteria count was recorded.

The activity of the compounds of the invention against such soil fungias Rhizoctonia solani and Fusarium solani was determined byincorporating the microorganisms into sterilized soil and 1 lb. portionsof this admixture were placed in quart jars. A small depression wasformed in the soil and filled with coarse sand. 1 ml. of 5% acetonesolution of the compound to be tested was introduced on to the sand andthe jar sealed. The contents of the container were then thoroughlyshaken and the infected soil seeded with representative commercial cropssuch as cotton or Pinto beans. After an interval of about 2 or 3 weeks,the plants were examined and the treated plants compared with thecontrols, having no treatment.

We claim:

1. A method of inhibiting the growth of microorganisms which comprisesapplying thereto a small but effective amount of a 2-halomethyl arylketone of the following formula:

2. A method of inhibiting the growth of microorganisms which comprisesapplying thereto a small but effective amount of Z-halomethyl naphthylketone of the following formula:

wherein X is selected from the class consisting of chlorine and bromine.

3. A method of inhibiting microorganism growth comprising, applying tosaid microorganism habitat a morebiologically effective amount of acompound of the formula:

wherein X is selected from the group Consisting of bromine and chlorine.

4. A method of inhibiting the growth of microorganisms comprisingapplying to said microorganism habitat a microbiologically ejjectiveamount of a compound of the formula:

5. A method of inhibiting the growth of microorganisms comprisingapplying to said microorganism habitat a microbiologically eflectiveamount of a compound of the formula:

o o-crns' References Cited by the Examiner The following references,cited by the Examiner, are of record in the patented file of this patentor the original patent.

UNITED STATES PATENTS Re. 26,009 5/1966 Buckman et a1. l62l61 2,901,3948/1959 Rosher l6730 3,021,256 2/1962 Bollenback et al. 162-161 FOREIGNPATENTS 1,330,953 6/1962 France.

ALBERT T. MEYERS, Primary Examiner. JULIAN S. LEVITT, Examiner.

GEORGE A. MENTIS, Assistant Examiner.

Z gz g? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.26,178 Dated March 21, 1967 Inventor(s) George E. Lukes and Thomas B.Williamson .4- It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

r- In Column 2, Compound 13, the formula should mac:

co-cn -sr In Column 3, Compound 24, the formula should read:

CO-CH -Br In Column 3, Compound 25, the formula should read:

OCH

73 3 UNITED STATES PATENT OFFICE Y CERTIFICATE OF CORRECTION Patent No.26 178 Dated March 21, 1967 Invemm-(S) George E. Lukes and Thomas B.Williamson It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

In Column 1, under line 47, the formula (II) should read as follows:

woo-W 41 In Column 1, Compound 20, the formula should read:

In Column 3, Compound 26, the formula should read:

H CO O-CH -Br (continued on Page 2) mg? UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Page 2 Patent; No. Dated March 21,

lnventoz-(s) George E. Lukes and Thomas B. Williamson identified patentIt is certified that error appears in the aboveshown below:

and that said Letters Patent are hereby corrected as In Columri 3,Compound 27, the formula should read:

HBCO CO-CH2-C1 OCH3 5; Cu. nova "I70 EAL) Attest:

EdwardMFl wllgh mm; x. 50mm, .112. Minimum- 01 Patents

